CN107629155A - A kind of polypropylene and its preparation method and application - Google Patents
A kind of polypropylene and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to field of olefin polymerisation, specifically provides a kind of polypropylene and its preparation method and application.The polyacrylic melt flow index MFR>30g/10min, isotactic index are 96 99.5wt%, and molecular weight distributing index MW/Mn is 3 5.5.The polyacrylic preparation method is included under olefin polymerization conditions, in the presence of a catalyst, propylene is polymerize to obtain polypropylene product, the catalyst contains catalytic component, alkyl aluminum compound and optional external electron donor, the catalytic component contains reacts obtained product by magnesium source, titanium source and internal electron donor, the internal electron donor contains phosphate compounds and diether compound, and the phosphorus content in the catalytic component in terms of P elements is not more than 0.06 weight %.The characteristics of polypropylene provided by the invention is with high isotactic index, high melt flow index and Narrow Molecular Weight Distribution.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of polypropylene, a kind of polyacrylic preparation method, by the party
Application of the polypropylene and the polypropylene that method is prepared in fiber and non-woven fabrics is prepared.
Background technology
Polypropylene possesses many merits, for example, density is low, bending modulus and fusing point are all higher, processing characteristics is good, tool
There are fabulous chemical stability, electrical insulating property, the propylene feedstocks needed for manufacture polypropylene cheap and easily-available etc..Although however, poly- third
Alkene material possesses these advantages, but in some fields, due to the characteristic of itself, it is referred to possessing higher melt flows
During number, isotactic index is relatively low；And isotactic index it is higher when, melt flow index is relatively low, i.e. can not obtain melt flow index compared with
High and isotactic index also higher polypropylene.In the prior art, when the isotactic index of acrylic polymers is 96-99.5wt%,
The melt flow index determined according to ASTM D1238-99 is only often 0.5-35 grams/10 minutes；And according to ASTM D1238-
When the melt flow index of 99 measure is 40-50 grams/10 minutes, the isotactic index of acrylic polymers is only 91-95wt%.Due to
Polyacrylic properties mutually pin down, and the raising of a performance indications is often possible to cause under another performance indications
Drop, therefore, change polyacrylic performance and remarkable.
Melt flow index is an important indicator of polypropylene material processing characteristics, such as：Extrusion or molding, wherein necessary
Polypropylene material is softened or melted.The polypropylene material of the low melt flow index obtained for initial polymerization must enter to advance
The modification of one step is to improve its processability.Carried out generally by the technology of control rheology, for example, can be by adding peroxidating
Thing reduces the molecular weight of polypropylene material, thus improves its mobility.But this processing method can bring some drawbacks,
Such as：Procedure of processing is added, causes manufacturing cost to rise；Organic peroxide is unstable and is difficult processing；Degradation reaction meeting
Produce poisonous accessory substance, such as tert-butyl alcohol.Therefore, it is restricted its application in some fields, such as food packaging applications.
Furthermore it is possible to polyacrylic performance, at present, O-phthalic are improved by using high performance polypropylene catalyst
Acid esters compound (plasticiser) is more conventional polypropylene catalyst internal electron donor, but studies and find, contains adjacent benzene two
The catalyst of formic ether compounds, because its capacity of orientation is inadequate, causes polymer when preparing high fusion index product
Isotactic index is relatively low, it is impossible to meet product requirement, and its to animal grow and reproductive system can cause serious harm,
Meanwhile the mankind may also be produced with similar influence.
At present, fiber and nonwoven are furnished with larger market prospects, and it is required to obtain using lower-cost catalyst
The polymer that molecular weight distribution is narrower, melt flow index is big and isotactic index is high, therefore, find without phthalic acid ester
The catalyst of (plasticiser) is current to obtain the polymer that molecular weight distribution is narrower, melt flow index is big and isotactic index is high
It is badly in need of the problem solved.
The content of the invention
The purpose of the present invention is the defects of overcoming prior art, there is provided a kind of to use what the catalyst without plasticiser obtained
Have polypropylene of high isotactic index, high melt flow index and Narrow Molecular Weight Distribution and its preparation method and application concurrently.
The invention provides a kind of polypropylene, the polyacrylic melt flow index MFR>30g/10min, isotactic index are
96-99.5wt%, molecular weight distributing index MW/ Mn is 3-5.5.
Present invention also offers a kind of polyacrylic preparation method, this method is included under olefin polymerization conditions, is being catalyzed
In the presence of agent, propylene is polymerize to obtain polypropylene product, the catalyst contain catalytic component, alkyl aluminum compound with
And optional external electron donor, the catalytic component contains reacts obtained product by magnesium source, titanium source and internal electron donor, its
In, the internal electron donor contains phosphate compounds and diether compound, using the gross weight of the catalytic component as
Benchmark, the phosphorus content in the catalytic component in terms of P elements are not more than 0.06 weight %.
Present invention also offers the polypropylene prepared by the above method.
The present inventor has been surprisingly found that in research process, during synthesis is polyacrylic, when the catalysis used
Internal electron donor contains diether compound and phosphate compounds simultaneously in agent component, and when with the catalytic component
Gross weight on the basis of, when the phosphorus content in the catalytic component in terms of P elements is not more than 0.06 weight %, enable to
Obtained polypropylene has the characteristics of high isotactic index, high melt flow index and Narrow Molecular Weight Distribution concurrently.In addition, the hair of the present invention
A person of good sense also found, a preferred embodiment of the invention, be used for when being prepared using diether compound as internal electron donor
During the catalytic component of olefinic polymerization, when adding micro phosphate, i.e. when the phosphate and diether compound
The mol ratio of dosage be 0.02-0.25：1st, it is preferably 0.04-0.15：When 1, it can be carried out between both internal electron donors
Cooperate perfectly with very much, so as to more effectively improve the hydrogen response of catalyst and vertical structure directionality, further improve poly-
The isotactic index and melt flow index of propylene simultaneously reduce its molecular weight distributing index.In addition, work as phosphoric acid in internal electron donor
When the mol ratio control of the dosage of ester type compound and diether compound is in above-mentioned preferable scope, urged what is finally given
The content of phosphate compounds present in agent is extremely small, so as to effectively avoid substantial amounts of phosphate compounds
Presence the problem of bringing.
In addition, the application present invention also offers above-mentioned polypropylene in fiber and non-woven fabrics is prepared.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of polypropylene, the polyacrylic melt flow index MFR>30g/10min, isotactic index are
96-99.5wt%, molecular weight distributing index MW/ Mn is 3-5.5.
Polyacrylic melt flow index MFR, isotactic index and molecular weight distributing index M of the present inventionW/ Mn can be with
Selected by the requirement to product, for example, the polyacrylic melt flow index MFR>50g/10min, isotactic index
For 96.5-98.5wt%, molecular weight distributing index MW/ Mn is 3.5-5.
According to a kind of embodiment of the present invention, the polyacrylic melt flow index MFR is 70-90g/
10min, isotactic index 97.5-98.5wt%, molecular weight distributing index MW/ Mn is 4-5.
Polyacrylic melt flow index MFR provided by the invention can be more than 30g/min, be preferably greater than 50g/min,
More preferably 70-90g/10min, such as can be 70-75g/10min, 75-80g/10min, 80-85g/10min or 85-
Arbitrary value between 90g/10min.
Polyacrylic isotactic index provided by the invention can be 96-99.5wt%, be preferably 96.5-98.5wt%, more
Preferably 97.5-98.5wt%, for example, can be between 97.5-98wt% or 98-98.5wt% arbitrary value.
Polyacrylic molecular weight distributing index provided by the invention can be carried out according to the polyacrylic concrete application occasion
Appropriate selection can be 3-5.5 disclosure satisfy that requirement is defined, be preferably 3.5-5, appointing between more preferably 4-5
Meaning value.
The melt flow index MFR determines according to ASTM D1238-99 method；The isotactic index is taken out using heptane
Formulation measure (heptane boiling extracting 6 hours), that is, the polymer samples for taking 2g to dry, be placed in extractor and extracted with boiling heptane
6 hours, afterwards, by residue drying to constant weight, resulting polymers weight (g) and 2 ratio were isotactic index；The molecule
Measure profile exponent MW/ Mn is determined using Shimadzu LC-10AT types gel permeation chromatograph (GPC), wherein, trichloro-benzenes is mobile phase,
Temperature is 150 DEG C.
Instant invention overcomes in the prior art when the polyacrylic melt flow index of preparation is higher, isotactic index compared with
Low, and when isotactic index is higher, the defects of melt flow index is relatively low, polypropylene provided by the invention is using being free of plasticiser
Catalyst preparation obtain, and the characteristics of with high isotactic index, high melt flow index and Narrow Molecular Weight Distribution.
Present invention also offers a kind of polyacrylic preparation method, this method is included under olefin polymerization conditions, is being catalyzed
In the presence of agent, propylene is polymerize to obtain polypropylene product, the catalyst contain catalytic component, alkyl aluminum compound with
And optional external electron donor, the catalytic component contains reacts obtained product, institute by magnesium source, titanium source and internal electron donor
State internal electron donor and contain phosphate compounds and diether compound, on the basis of the gross weight of the catalytic component,
Phosphorus content in the catalytic component in terms of P elements is not more than 0.06 weight %.
A preferred embodiment of the invention, on the basis of the gross weight of the catalytic component, the catalysis
Using the phosphorus content that P elements are counted as 0.002-0.05 weight %, preferably 0.005-0.04 weight % in agent component.Using this kind
Preferred embodiment, the post processing that there are problems that bringing of substantial amounts of phosphate compounds was both avoided, can also ensure two
The synergy of ether compound and phosphate compounds, it can further improve the hydrogen response of catalyst and vertical structure
Directionality, while catalytic component is applied to obtain in olefinic polymerization and has high isotactic index, high melt flow index concurrently
And the polymer of the characteristics of Narrow Molecular Weight Distribution.
In the present invention, the content of P elements can be measured using X-ray fluorescence spectra analytic approach in catalytic component.
According to the present invention, just can be produced when the internal electron donor contains diether compound and phosphate compounds
Raw certain cooperative effect, on the basis of the dosage of the internal electron donor, preferably phosphate compounds and two ethers chemical combination
Total dosage of thing is 70-100 weight %, more preferably more preferably 80-100 weight %, 90-100 weight %, most preferably
For 100 weight %.
The present inventor, which studies, to be found, when relative to every mole of diether compound, the use of phosphate compounds
Measure as 0.02-0.25 moles, at preferably 0.04-0.15 moles, both, which can cooperate with, allocates more preferably, so as to obtain hydrogen adjust it is quick
The perceptual and vertical more preferable catalyst of structure directionality, and then cause obtained polypropylene to have higher isotactic index and melt flows concurrently
The characteristics of index and narrower molecular weight distribution.
The present invention has no particular limits to the content of magnesium, titanium and internal electron donor in catalytic component, can be this
Content arbitrary value in the conventional catalyst components of field, it is preferable that in terms of the titanium elements of every parts by weight, magnesium elements are 2-15 weight
Part, preferably 3-12 parts by weight, more preferably 4-10 parts by weight；Internal electron donor is 2-10 parts by weight, and preferably 3-8 is heavy
Measure part, more preferably 4-7 parts by weight.
In the present invention, titanium elements, the content of magnesium elements can use X-ray fluorescence spectra analytic approach in catalytic component
Measure；The content of internal electron donor (phosphate compounds and diether compound) passes through chromatogram and mass spectrum in catalytic component
Analysis obtains.
The present invention is also not particularly limited to the species of the phosphate compounds, can be that various can be used as is used
Under the phosphate compounds of the catalyst internal electron donor of olefinic polymerization, preferable case, the phosphate compounds tool
There is the structure shown in formula (1),
Wherein, R13、R14And R15It is each independently selected from C1-C4Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20
Aryl, C7-C20Alkaryl and C7-C20Aralkyl in one kind, in the aryl, alkaryl and aralkyl on phenyl ring
Hydrogen atom is optionally substituted by halogen atom；Further preferred R13、R14And R15It is each independently selected from C1-C4Straight or branched alkane
Base, C3-C12Cycloalkyl, C6-C12Aryl, C7-C12Alkaryl and C7-C12Aralkyl in one kind, the aryl, alkane
Hydrogen atom in aryl and aralkyl on phenyl ring is optionally substituted by halogen atom；Still more preferably R13、R14And R15Independently of one another
Selected from C1-C4Straight or branched alkyl, C3-C6Cycloalkyl, C6-C8Aryl, C7-C8Alkaryl and C7-C8Aralkyl
In one kind, the hydrogen atom in the aryl, alkaryl and aralkyl on phenyl ring optionally substitutes by halogen atom；Such as R13、R14With
R15It is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, cyclopropyl, ring
Butyl, cyclopenta, cyclohexyl, phenyl, tolyl, 3,5-dimethylphenyl, ethylbenzene, benzyl, methyl-benzyl or phenethyl.
Preferably, the phosphate compounds are selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate
Phenyl ester, tricresyl phosphate, IPPP, tripotassium phosphate epoxide phenyl ester, phosphoric acid phenyl dimethyl ester, tricresyl phosphate base
Dibutyl ester, p isopropylbenzoic acid phenyl dimethyl ester, p isopropylbenzoic acid diethylamino phenyl ester, p isopropylbenzoic acid phenyl dibutyl ester, phosphoric acid phenyl diformazan
Tolyl dibutyl ester, phosphoric acid are to isopropylbenzene between phenyl ester, phosphoric acid phenyl 6-diisopropyl benzene ester, phosphoric acid p-methylphenyl dibutyl ester, phosphoric acid
Base dimethyl ester, phosphoric acid are to cumenyl diethylester, phosphoric acid to tert-butyl-phenyl dimethyl ester and phosphoric acid o-tolyl to two 2-methyl-2-phenylpropanes
At least one of base ester.
Most preferably, the phosphate compounds are tributyl phosphate.
According to the present invention, the diether compound can be it is various can be used as be used for olefinic polymerization catalyst in give
The diether compound of electron, preferably described diether compound are selected from least one in diether compound shown in formula (2)
Kind,
R1R2C(CH2OR3)(CH2OR4) formula (2)
Wherein, R1And R2It is each independently selected from hydrogen, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20
Aryl, C7-C20Aralkyl and C7-C20Alkaryl in one kind, optionally bonded cyclization between group；R3And R4Each
Independently selected from C1-C10Alkyl.
Preferably, described diether compound is selected from 2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2- isopropyls
Base -1,3- dimethoxy propanes, 2- butyl -1,3- dimethoxy propanes, 2- sec-butyl -1,3- dimethoxy propanes, 2- hexamethylenes
Base -1,3- dimethoxy propanes, 2- phenyl -1,3- dimethoxy propanes, 2- (2- phenylethyls) -1,3- dimethoxy propanes,
2- (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- (p- chlorphenyl) -1,3- dimethoxy propanes, 2- (diphenylmethyls
Base) -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2,2- bicyclopentyl -1,3- dimethoxys
Propane, 2,2- diethyl -1,3- dimethoxy propanes, 2,2- dipropyl -1,3- dimethoxy propanes, 2,2- diisopropyl -1,
3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxy propanes, 2- methyl-2-propyl -1,3- dimethoxy propanes, 2-
Methyl -2- benzyl -1,3- dimethoxy propanes, 2- methyl -2- ethyl -1,3- dimethoxy propanes, 2- methyl -2- isopropyls -
1,3- dimethoxy propanes, 2- methyl -2- phenyl -1,3- dimethoxy propanes, 2- methyl -2- cyclohexyl -1,3- dimethoxys
Double (2- the cyclohexyl-ethyls) -1,3- dimethoxy propanes of propane, 2,2-, 2- methyl -2- isobutyl group -1,3- dimethoxy propanes,
2- methyl -2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- hexichol
Double (the cyclohexyl methyl) -1,3- dimethoxies of base -1,3- dimethoxy propanes, 2,2- dibenzyl -1,3- dimethoxy propanes, 2,2-
Base propane, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2- (1- methyl butyls) -2- isopropyl -1,3- dimethoxies
Base propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2- phenyl -2- isopropyl -1,3- dimethoxy propanes, 2-
Phenyl -2- sec-butyl -1,3- dimethoxy propanes, 2- benzyl -2- isopropyl -1,3- dimethoxy propanes, 2- cyclopenta -2-
Isopropyl -1,3- dimethoxy propanes, 2- cyclopenta -2- sec-butyl -1,3- dimethoxy propanes, 2- cyclohexyl -2- isopropyls
Base -1,3- dimethoxy propanes, 2- cyclohexyl -2- sec-butyl -1,3- dimethoxy propanes, 2- isopropyl -2- sec-butyl -1,
In 3- dimethoxy propanes, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes and 9,9- dimethoxy-methyl fluorenes
It is at least one.
Most preferably, the diether compound is 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes.
In the present invention, when preferably by tributyl phosphate and 2- isopropyl -2- isopentyl -1,3- dimethoxy propane conducts
When internal electron donor is used cooperatively, the hydrogen response of catalyst and vertical structure directionality can be particularly effectively improved, and then make
The polypropylene that must be obtained has the characteristics of high isotactic index, high melt flow index and Narrow Molecular Weight Distribution concurrently.
A preferred embodiment of the invention, the mode in the magnesium source, titanium source and internal electron donor reaction are：Will
Magnesium source and titanium source carry out haptoreaction, and one before and after, during the magnesium source and titanium source carry out haptoreaction or
Internal electron donor is added in multiple periods.
The haptoreaction of the magnesium source and titanium source can be carried out according to mode same as the prior art, for example, can incite somebody to action
Titanium source is cooled to less than 0 DEG C (being preferably -5 to -25 DEG C), then adds magnesium source, and be stirred 10-60 points at such a temperature
Clock, reaction temperature (i.e. about 60-130 DEG C) is warming up to afterwards, and 0.5-10 hours are maintained under the reaction temperature.It is described to contain phosphorus
The internal electron donor compound of acid esters compound and diether compound is before the haptoreaction of the magnesium source and titanium source, the phase
Between and add one or more of afterwards in the period.Period before the haptoreaction of the magnesium source and titanium source refers to
After the magnesium source is added in reactor and the period before reaction temperature is warming up to.At least contain phosphate compounds
It can together add, can also be added separately to each leisure different period with the internal electron donor of diether compound.
Under preferable case, period addition before reactions is at least electric containing being given in phosphate compounds and diether compound
Daughter.
In accordance with the present invention it is preferred that the dosage in the magnesium source in terms of magnesium elements, the titanium source in terms of titanium elements and internal electron donor
Mol ratio be 1：20-150：0.1-0.9, more preferably 1：30-120：0.15-0.6.
In the present invention, the magnesium source can be the chemical combination containing magnesium of the existing various catalyst that can be used in olefinic polymerization
Thing, for example, the magnesium source can be magnesium halide, the alcoholates of magnesium or halogenated alcoholate and adduct of magnesium halides carrier etc.；It is described
Magnesium halide for example can be magnesium chloride and/or magnesium bromide；The alcoholates of the magnesium for example can be diethoxy magnesium；The magnesium
Halogenated alcoholate for example can be chlorination magnesium ethylate；The species of the adduct of magnesium halides carrier is that those skilled in the art are public
Know, for example, can be CN1091748A, CN101050245A, CN101486722A, 201110142357.X,
Adduct of magnesium halides carrier disclosed in the grades of 201110142156.X and 201110142024.7, and will be related disclosed in these patents
Content is all incorporated in the present application as reference.The specific preparation method of the adduct of magnesium halides carrier can include following step
Suddenly：The each component for forming adduct of magnesium halides is mixed, temperature reaction generation adduct of magnesium halides melt, reaction temperature is
90-140 DEG C, it is put into decentralized medium after high shear forces in cooling medium, forms Spherical magnesium halide adduct particle, warp
Washing, ball type carrier is obtained after drying, internal electron donor can be selectively added in the process or afterwards.The high shear
Effect can use conventional method to obtain, such as high-speed mixing method (such as CN1330086), spray-on process (such as US6020279) and super
Gravity revolving bed (such as CN1580136A) and mulser method (CN1463990A).The decentralized medium for example can be that hydro carbons is lazy
Property solvent, the one or more in such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil.The cooling medium for example can be with
Selected from pentane, hexane, heptane, petroleum ether, raffinate oil etc. in one or more.
According to the present invention, in the preparation process for the catalytic component of olefinic polymerization, titanium source can be this area
Conventional selection, for example, it is Ti (OR ') that the titanium source, which can be formula,3-aZaAnd/or Ti (OR ')4-bZbMaterial, wherein, R ' is
C1-C20Alkyl, Z F, Cl, Br or I, a be 1-3 integer, b be 1-4 integer.Under preferable case, the titanium source is tetrachloro
Change titanium, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy titanium trichloride, three ethoxies
One or more in base titanium chloride, diethoxy titanium chloride, ethyoxyl titanium trichloride and titanium trichloride.
In catalyst of the present invention, the alkyl aluminum compound can be various alkyl commonly used in the art
Aluminium compound, for example, the formula of the alkyl aluminum compound can be AlR16R16′R16", wherein, R16、R16' and R16" each solely
It is on the spot C1-C8Alkyl, and wherein one or two group can be halogen, and the hydrogen on alkyl can also be optionally substituted by halogen；Institute
State C1-C8The instantiation of alkyl can include but is not limited to：Methyl, ethyl, propyl group, normal-butyl, isobutyl group, amyl group, oneself
Base, n-heptyl, n-octyl, the halogen can be fluorine, chlorine, bromine, iodine.Specifically, the alkyl aluminum compound can for example select
From triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine
Di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, the aluminium ethide of dichloro one, the aluminium isobutyl of dichloro one, the n-butylaluminum of dichloro one and dichloro one
One or more in n-hexyl aluminium.
In catalyst of the present invention, the external electron donor can be various outer electrons commonly used in the art
Body, for example, the external electron donor can be selected from carboxylic acid, carboxylic acid anhydrides, carboxylate, ketone, ether, alcohol, lactone, organic phosphorus compound and
At least one of organo-silicon compound.Preferably, the external electron donor is to be containing at least one Si-OR keys and formula
(R17)x(R18)ySi(OR19)zSilicon compound, wherein, R17、R18And R19For C1-C18Alkyl, optionally contain hetero atom, x
Each stand alone as 0-2 integer with y, z is 1-3 integer, and x, y and z and be 4.Preferably, R17、R18For C3-C10Alkane
Base, cycloalkyl, optionally contain hetero atom；R19For C1-C10Alkyl, optionally contain hetero atom.Specifically, it is described outer to electricity
Daughter can for example be selected from Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy
Silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, bicyclopentyl
Dimethoxysilane, 2- ethyl piperidine base -2- t-butyldimethoxysilanes, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidines
At least one of base dimethoxysilane and (1,1,1-, three fluoro- 2- propyl group)-methyl dimethoxysilane.
Typically also, in catalyst of the present invention, the catalytic component in terms of titanium elements and with aluminium member
The mol ratio of the alkyl aluminum compound dosage of element meter can be 1：1-2000, preferably 1：20-500；The outer electron
The mol ratio of body and the alkyl aluminum compound dosage in terms of aluminium element can be 1：2-200, preferably 1：2.5-100.
According to the present invention, when the catalyst is used for olefinic polymerization, the catalytic component, alkyl aluminum compound and
External electron donor can be separately added into polymer reactor, added after can also mixing in polymer reactor, can also use the industry public
The prepolymerization method known will be added in polymer reactor after alkene pre-polymerization.
A preferred embodiment of the invention, by catalytic component, alkyl aluminum compound and external electron donor
Compound before polymerization, carries out pre-contact reaction, and pre-contact reaction temperature can be -15 DEG C to 40 DEG C, be preferably 0-20
DEG C, the pre-contact reaction time can be 0.5-60min, be preferably 1-20min.Catalysis can be significantly improved by carrying out pre-contact reaction
The polymerization activity of agent and polyacrylic apparent density, while strengthen the anti-impurity interference performance of catalyst active center, and then
Reduce the broken of ash content in polypropylene and PP GRANULES.
A preferred embodiment of the invention, pre-contact reaction after, before polymerisation, preferably by catalyst with
Propylene carries out prepolymerization.A small amount of hydrogen or non-hydrogenation can be added during prepolymerization, prepolymerization temperature can be with
For 10-70 DEG C, preferably 15-30 DEG C, prepolymerization time can be 0-60min, preferably 4-30min.
According to the present invention, the polymerisation can be carried out according to existing various methods, specifically, can be in indifferent gas
Under the protection of body, in liquid monomer or atent solvent containing polymerized monomer, or in the gas phase, or pass through the group in liquid phase
Close polymerization technique and carry out polymerisation.The temperature of the polymerisation can be typically 0-150 DEG C, be preferably 60-90 DEG C.It is described
The pressure of polymerisation can be normal pressure or higher；Such as can be 0.01-10MPa, preferably 0.01-6MPa, it is more preferably
0.1-4MPa.The pressure of the present invention refers both to gauge pressure.In the course of the polymerization process, hydrogen can be used as polymer molecular weight conditioning agent and be added to
To adjust the molecular weight of polymer and melt flow index in reaction system, the concentration of hydrogen can be more than or equal to 1500ppm,
Preferably greater than or equal to 2500ppm, most preferably 2500-4500ppm.The polymerization time of propylene and catalyst is preferably 0.5-6h,
More preferably 1-2h.In addition, in the polymerization process of alkene, the inert gas, the species of solvent and dosage are this
Known in art personnel, it will not be described in great detail herein.
In accordance with the present invention it is preferred that the polyacrylic preparation method also includes：Polymerization is produced after polymerisation terminates
Thing is granulated.Specifically, the additives such as antioxidant, stabilizer are preferably added in granulation process.The antioxidant, stabilizer
Species and dosage Deng additive are known to the skilled person, and will not be described in great detail herein.
Present invention also offers the polypropylene being prepared by above-mentioned polyacrylic preparation method.
In addition, the application present invention also offers polypropylene in fiber and non-woven fabrics is prepared.
The present invention will be described in further detail by following examples below.
In following examples and comparative example：
The melt flow index MFR determines according to ASTM D1238-99 method；The isotactic index is taken out using heptane
Formulation measure (heptane boiling extracting 6 hours), that is, the polymer samples for taking 2g to dry, be placed in extractor and extracted with boiling heptane
6 hours, afterwards, by residue drying to constant weight, resulting polymers weight (g) and 2 ratio were isotactic index；The molecule
Measure profile exponent MW/ Mn is determined using Shimadzu LC-10AT types gel permeation chromatograph (GPC), wherein, trichloro-benzenes is mobile phase,
Temperature is 150 DEG C.
Embodiment 1
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
(1) catalytic component is prepared
In 300ml glass reaction bottle, add 90ml (820mmol) titanium tetrachloride and be cooled to -20 DEG C, will be with magnesium
The 37mmol of element meter magnesium halide carrier (as disclosed in CN1330086A embodiments 1 prepared by method) is added thereto, Ran Housheng
Temperature to 110 DEG C, and in temperature-rise period add 0.3mmol tributyl phosphate and 7.3mmol 2- isopropyl -2- isopentyl -
1,3- dimethoxy propane, liquid is filtered off after maintaining 30min at 110 DEG C, is washed 2 times with titanium tetrachloride, 5 is washed with hexane
It is secondary, the catalytic component Cat-1 for olefinic polymerization is obtained after vacuum drying.
Measured using X-ray fluorescence spectra analytic approach, used in the catalytic component Cat-1 of olefinic polymerization in terms of P elements
Phosphorus content be 0.011 weight %, using the Ti content that titanium elements are counted as 2.6 weight %.
(2) polypropylene is prepared
By catalytic component Cat-1, triethyl aluminum and the Cyclohexyl Methyl Dimethoxysilane (catalyst in terms of titanium elements
The mol ratio of component Cat-1 and the triethyl aluminum counted using aluminium element is 1：200；Cyclohexyl Methyl Dimethoxysilane with aluminium member
The mol ratio of the triethyl aluminum of element meter is 1:10) at 10 DEG C after pre-contact 15min, it is added into pre-polymerization reactor and carries out in advance
Polymerisation, the prepolymerization are carried out under propylene liquid-phase bulk environment, and prepolymerization temperature is 17 DEG C, and prepolymerization time is
15min, obtained mixture is then continually introduced into annular-pipe reactor and carries out propylene polymerization, polymeric reaction temperature 70
DEG C, reaction pressure 3.5MPa, hydrogen, the concentration (being detected by on-line chromatograph) of hydrogen are passed through in the charging of annular-pipe reactor
For 3800ppm, reaction time 1h, cool afterwards, release, discharging, weigh and analyze after gained Noblen is dried, tie
Fruit is as shown in table 1.
Embodiment 2
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and prepares polypropylene, unlike, added in temperature-rise period
Tributyl phosphate and the amounts of 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes be respectively 1mmol and 10mmol, obtain
Catalytic component Cat-2 for olefinic polymerization.
Measured using X-ray fluorescence spectra analytic approach, used in the catalytic component Cat-2 of olefinic polymerization in terms of P elements
Phosphorus content be 0.025 weight %, using the Ti content that titanium elements are counted as 2.5 weight %.
Weigh and analyze after gained Noblen is dried, as a result as shown in table 1.
Embodiment 3
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and prepares polypropylene, unlike, added in temperature-rise period
Tributyl phosphate and the amounts of 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes be respectively 1.1mmol and 7.3mmol, obtain
To the catalytic component Cat-3 for olefinic polymerization.
Measured using X-ray fluorescence spectra analytic approach, used in the catalytic component Cat-3 of olefinic polymerization in terms of P elements
Phosphorus content be 0.04 weight %, using the Ti content that titanium elements are counted as 2.6 weight %.
Weigh and analyze after gained Noblen is dried, as a result as shown in table 1.
Embodiment 4
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, the phosphorus added in temperature-rise period
The amount of sour tributyl and 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes is respectively 0.15mmol and 7.3mmol, is obtained
Catalytic component Cat-4 for olefinic polymerization.
Measured using X-ray fluorescence spectra analytic approach, used in the catalytic component Cat-4 of olefinic polymerization in terms of P elements
Phosphorus content be 0.005 weight %, using the Ti content that titanium elements are counted as 2.7 weight %.
Weigh and analyze after gained Noblen is dried, as a result as shown in table 1.
Embodiment 5
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, added in temperature-rise period
0.3mmol IPPP and 7.3mmol 9,9- dimethoxy-methyl fluorenes, and it is added without 0.3mmol phosphoric acid
2- isopropyl -2- isopentyl -1,3- dimethoxy propanes of tributyl and 7.3mmol, obtain the catalyst for olefinic polymerization
Component Cat-5, wherein using the phosphorus content that P elements are counted as 0.009 weight %, using the Ti content that titanium elements are counted as 2.6wt%；Will
Gained Noblen is weighed and analyzed after drying, as a result as shown in table 1.
Embodiment 6
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, the concentration of hydrogen is 3300ppm,
The analysis result for obtaining Noblen is as shown in table 1.
Embodiment 7
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, the concentration of hydrogen is 2800ppm,
The analysis result for obtaining Noblen is as shown in table 1.
Embodiment 8
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, the concentration of hydrogen is 2500ppm,
The analysis result for obtaining Noblen is as shown in table 1.
Embodiment 9
The present embodiment is used for illustrating according to polypropylene of the present invention and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, the concentration of hydrogen is 2300ppm,
The analysis result for obtaining Noblen is as shown in table 1.
Comparative example 1
This comparative example is used to illustrate reference polypropylene and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, in the preparation of catalytic component
Cheng Zhong, the tributyl phosphate are substituted with 2- isopropyl -2- isopentyl -1,3- dimethoxy propane of identical weight part, obtained
Catalytic component DCat-1 for olefinic polymerization；Weigh and analyze after gained Noblen is dried, as a result such as the institute of table 1
Show.
Comparative example 2
This comparative example is used to illustrate reference polypropylene and preparation method thereof.
Method according to comparative example 1 prepares catalytic component and polypropylene, unlike, the concentration of hydrogen is 3300ppm,
The analysis result for obtaining Noblen is as shown in table 1.
Comparative example 3
This comparative example is used to illustrate reference polypropylene and preparation method thereof.
Method according to comparative example 1 prepares catalytic component and polypropylene, unlike, the concentration of hydrogen is 2300ppm,
The analysis result for obtaining Noblen is as shown in table 1.
Comparative example 4
This comparative example is used to illustrate reference polypropylene and preparation method thereof.
Method according to embodiment 2 prepares catalytic component and polypropylene, unlike, in the preparation in catalytic component
During, the tributyl phosphate is substituted with 2- isopropyl -2- isopentyl -1,3- dimethoxy propane of identical weight part, is obtained
To the catalytic component DCat-4 for olefinic polymerization；Weigh and analyze after gained Noblen is dried, as a result such as the institute of table 1
Show.
Comparative example 5
This comparative example is used to illustrate reference polypropylene and preparation method thereof.
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, in the preparation of catalytic component
Cheng Zhong, the tributyl phosphate of addition and the amount of 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes be respectively 2.2mmol and
7.3mmol, the catalytic component DCat-5 for olefinic polymerization is obtained, wherein using the phosphorus content that P elements are counted as 0.07 weight
Measure %；Weigh and analyze after gained Noblen is dried, as a result as shown in table 1.
Comparative example 6
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, in the preparation of catalytic component
Cheng Zhong, 2- isopropyls -2- isopentyl -1,3- dimethoxy propane 2,4- glycol dibenzoates of identical weight part
Substitute, obtain the catalytic component DCat-6 for olefinic polymerization；Weigh and analyze after gained Noblen is dried, as a result
As shown in table 1.
Comparative example 7
Method according to embodiment 1 prepares catalytic component and polypropylene, unlike, the catalytic component Cat-1
With the DQ catalytic components (abbreviation produced purchased from Sinopec Ao Da catalyst branch company of identical weight part：DCat-7, inside give
Electron is diisobutyl phthalate) substitute, weigh and analyze after gained Noblen is dried, as a result such as the institute of table 1
Show.
Comparative example 8
This comparative example is used to illustrate reference polypropylene and preparation method thereof.
Method according to embodiment 9 prepares catalytic component and polypropylene, unlike, the catalytic component Cat-1
With the DQ catalytic components (abbreviation produced purchased from Sinopec Ao Da catalyst branch company of identical weight part：DCat-8, inside give
Electron is diisobutyl phthalate) substitute, weigh and analyze after gained Noblen is dried, as a result such as the institute of table 1
Show.
Table 1
The present invention obtained under different hydrogen concentration poly- third is can be seen that from embodiment 1-9 and comparative example 1-8 result
Alkene is not on the basis of reducing isotactic index and not increasing molecular weight distribution, additionally it is possible to improves melt index, i.e. can have height concurrently
Isotactic index and melt flow index and narrow molecular weight distribution, under preferable case, isotactic index is up to 98.4wt%, melts
Melt index and be up to 90g/10min, molecular weight distributing index MW/ Mn is 4.2, and the present invention realizes polypropylene isotactic index and melting
The common raising of index, and the catalyst that the present invention uses does not contain phthalic acid ester (plasticiser), is more beneficial for poly- third
Application of the alkene in each field, the application particularly in fiber and bonded fabric product.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (14)
- A kind of 1. polypropylene, it is characterised in that the polyacrylic melt flow index MFR>30g/10min, isotactic index 96- 99.5wt%, molecular weight distributing index MW/ Mn is 3-5.5.
- 2. polypropylene according to claim 1, wherein, the polyacrylic melt flow index MFR>50g/10min, isotactic Index is 96.5-98.5wt%, molecular weight distributing index MW/ Mn is 3.5-5.
- 3. polypropylene according to claim 1 or 2, wherein, the polyacrylic melt flow index MFR is 70-90g/ 10min, isotactic index 97.5-98.5wt%, molecular weight distributing index MW/ Mn is 4-5.
- 4. a kind of polyacrylic preparation method, this method are included under olefin polymerization conditions, in the presence of a catalyst, propylene is entered Row polymerization obtains polypropylene product, and the catalyst contains catalytic component, alkyl aluminum compound and optional outer electron Body, the catalytic component contains reacts obtained product by magnesium source, titanium source and internal electron donor, it is characterised in that in described Electron donor contains phosphate compounds and diether compound, described on the basis of the gross weight of the catalytic component Phosphorus content in catalytic component in terms of P elements is not more than 0.06 weight %.
- 5. preparation method according to claim 4, wherein, it is described to urge on the basis of the gross weight of the catalytic component Using the phosphorus content that P elements are counted as 0.002-0.05 weight %, preferably 0.005-0.04 weight % in agent component.
- 6. preparation method according to claim 4, wherein, the mode in the magnesium source, titanium source and internal electron donor reaction is： The magnesium source and titanium source are subjected to haptoreaction, and before and after, during the magnesium source and titanium source carry out haptoreaction Internal electron donor is added in one or more periods.
- 7. preparation method according to claim 4, wherein, on the basis of the dosage of the internal electron donor, the phosphoric acid Total dosage of ester type compound and diether compound is 70-100 weight %.
- 8. preparation method according to claim 4, wherein, relative to diether compound every mole described, the phosphoric acid The dosage of ester type compound is 0.02-0.25 moles, preferably 0.04-0.15 moles.
- 9. preparation method according to claim 4, wherein, the magnesium source in terms of magnesium elements, the titanium source in terms of titanium elements with it is interior The mol ratio of the dosage of electron donor is 1：20-150：0.1-0.9, preferably 1：30-120：0.15-0.6.
- 10. according to the preparation method described in any one in claim 4-9, wherein, the phosphate compounds have formula (1) structure shown in,Wherein, R13、R14And R15It is each independently selected from C1-C4Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Virtue Base, C7-C20Alkaryl and C7-C20Aralkyl in one kind；Preferably, the phosphate compounds be selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, Tricresyl phosphate, IPPP, tripotassium phosphate epoxide phenyl ester, phosphoric acid phenyl dimethyl ester, the fourth of tricresyl phosphate base two Ester, p isopropylbenzoic acid phenyl dimethyl ester, p isopropylbenzoic acid diethylamino phenyl ester, p isopropylbenzoic acid phenyl dibutyl ester, phosphoric acid phenyl diformazan phenyl ester, Tolyl dibutyl ester, phosphoric acid are to cumenyl diformazan between phosphoric acid phenyl 6-diisopropyl benzene ester, phosphoric acid p-methylphenyl dibutyl ester, phosphoric acid Ester, phosphoric acid are to cumenyl diethylester, phosphoric acid to tert-butyl-phenyl dimethyl ester and phosphoric acid o-tolyl in two 2-methyl-2-phenylpropane base esters At least one.
- 11. according to the preparation method described in any one in claim 4-9, wherein, the diether compound is selected from formula (2) At least one of shown diether compound,R1R2C(CH2OR3)(CH2OR4) formula (2)Wherein, R1And R2It is each independently selected from hydrogen, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Virtue Base, C7-C20Aralkyl and C7-C20Alkaryl in one kind, R3And R4It is each independently selected from C1-C10Alkyl；Preferably, the diether compound is selected from 2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2- isopropyls -1,3- Dimethoxy propane, 2- butyl -1,3- dimethoxy propanes, 2- sec-butyl -1,3- dimethoxy propanes, 2- cyclohexyl -1,3- Dimethoxy propane, 2- phenyl -1,3- dimethoxy propanes, 2- (2- phenylethyls) -1,3- dimethoxy propanes, 2- (2- rings Hexyl ethyl) -1,3- dimethoxy propanes, 2- (p- chlorphenyl) -1,3- dimethoxy propanes, 2- (diphenyl methyl) -1,3- Dimethoxy propane, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2,2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- Diethyl -1,3- dimethoxy propanes, 2,2- dipropyl -1,3- dimethoxy propanes, 2,2- diisopropyl -1,3- dimethoxys Propane, 2,2- dibutyl -1,3- dimethoxy propanes, 2- methyl-2-propyl -1,3- dimethoxy propanes, 2- methyl -2- benzyls Base -1,3- dimethoxy propanes, 2- methyl -2- ethyl -1,3- dimethoxy propanes, 2- methyl -2- isopropyl -1,3- dimethoxies Base propane, 2- methyl -2- phenyl -1,3- dimethoxy propanes, 2- methyl -2- cyclohexyl -1,3- dimethoxy propanes, 2,2- are double (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- methyl -2- isobutyl group -1,3- dimethoxy propanes, 2- methyl -2- (2- Ethylhexyl) -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes, 2,2- diphenyl -1,3- diformazans Double (the cyclohexyl methyl) -1,3- dimethoxy propanes of epoxide propane, 2,2- dibenzyl -1,3- dimethoxy propanes, 2,2-, 2- are different Butyl -2- isopropyl -1,3- dimethoxy propanes, 2- (1- methyl butyls) -2- isopropyl -1,3- dimethoxy propanes, 2- are different Propyl group -2- isopentyl -1,3- dimethoxy propanes, 2- phenyl -2- isopropyl -1,3- dimethoxy propanes, 2- phenyl -2- sec- Butyl -1,3- dimethoxy propanes, 2- benzyl -2- isopropyl -1,3- dimethoxy propanes, 2- cyclopenta -2- isopropyls -1,3- Dimethoxy propane, 2- cyclopenta -2- sec-butyl -1,3- dimethoxy propanes, 2- cyclohexyl -2- isopropyl -1,3- dimethoxies Base propane, 2- cyclohexyl -2- sec-butyl -1,3- dimethoxy propanes, 2- isopropyl -2- sec-butyl -1,3- dimethoxys third At least one of alkane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes and 9,9- dimethoxy-methyl fluorenes.
- 12. preparation method according to claim 4, wherein, the catalytic component in terms of titanium elements and with aluminium element The mol ratio of the alkyl aluminum compound dosage of meter is 1：1-2000, preferably 1：20-500；The external electron donor and with The mol ratio of the alkyl aluminum compound dosage of aluminium element meter is 1：2-200, preferably 1：2.5-100.
- 13. the polypropylene prepared as the method described in any one in claim 4-12.
- 14. application of the polypropylene in claim 1-3 and 13 described in any one in fiber and non-woven fabrics is prepared.
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